Characterization of the Plasma Chemistry and Film Composition of PECVD Silicon Nitride Deposited from Silane-Nitrogen and Silane-Ammonia Mixtures with Argon Additions

Silicon nitride films deposited from silane-nitrogen and silane-ammonia mixtures by PECVD contain large amounts of hydrogen. We have determined that adding argon to the gas mixture reduces the amount of hydrogen in the resulting films. Differences in film composition are obviously due to changes in the chemistry of the discharge which was characterized by line-of-sight mass spectrometry, optical emission spectroscopy and plasma double probe measurements. Substrate temperature was fixed at 325°C, pressure was 500 mtorr, the RF power was 0.25 watts cm−2, the silane to nitrogen ratio was varied from 0.003 to 0.02, the silane to ammonia ratio was varied from 0.01 to 0.5, and the argon additions were 10% of the total gas flow. Argon additions to the discharge increased the plasma density in both nitrogen and ammonia plasmas. Optical emission from N2 and Si-H species increased upon the addition of 10% argon to the silane-nitrogen discharge, whereas the N-H emission decreased upon addition of argon to the silane-ammonia discharge. Infrared transmission spectra of films deposited with and without argon show no change in peak position or intensity of Si-H and N-H absorption bands in the spectral range studied, despite a large (over 20%) reduction in hydrogen content, as determined by nuclear profiling, upon the addition of argon. These results suggest that a substantial fraction of the hydrogen in the films is not infrared active. We propose that the reduction in hydrogen content is due to bombardment of the growing film by argon ions, which sputter the adsorbed hydrogen molecules.